Vat dye printing



time

United States Patent 2,907,624 VAT DYE PRINTING Arthur K. Saville, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 5, 1957 Serial No. 676,429 g 7 Claims. (Cl. 8-70) This invention relates to vat dye printing, and more particularly to an improved process for the application of vat dyes to textile materials by printing processes in which the vat color is applied to the fabric in the form of a dispersion in a water-in-oilemulsion. This is a continuation-in-part of my co pending application Serial No. 609,347, filed September 12, 1956 (now abandoned). r

.In the usual methods of printing textile materials with vat dyes, the vat color is dispersed in an aqueous printing paste together with water-soluble thickeners, in which paste is also incorporated the reducing agentand alkali usually in the form of an alkali metal sulfoxylate and an alkali metal carbonate. On the passing of the textile printed with this'paste into an air-free steam atmosphere, the color is converted to the leuco form and fixed into the cellulose fibers, after which the dye is reoxidized on the fiber and the goods washed to free it from the carrier and decomposition products of the reducing agent and alkali.

Alternatively, the aqueous suspension of the dye paste together with a thickener may be printed on the textile materials, and, after drying, these materials are passed rapidly through a chemical bath consisting of caustic alkali and sodium hydrosulfite directly into an air-free steamer where the dye is reduced and fixed in the fiber and then reoxidized in the usual manner.

.To obviate the use of the more expensive vat dyes, methods of printing textile materials have been devised wherein a color in pigment form is dispersed in nonaqueous vehicles containing heat convertible resins, so that after printing these inks on textile materials and heating, the color is fixed to the fibers by the bonding action of the resins employed. This type of print, while having reasonable fastness to washing in pastel and light shades, suffers from severe loss of color value when printed in medium and heavy shades and subjected to washing. This type of print is particularly deficient when subjected alternatively to light exposure and washing, due to degradation of the bonding resin under these conditions. In these prints it is obvious that the color itself is not made an integral part of the textile material.

It is an object of the present invention to provide a I new and improved process for printing textile materials with vat dyes in which high color value can be obtained from the vat dye which itself is reduced and attached to the fiber in the same manner as when the dye is fixed by conventional vat printing procedures. A more'specific object of the inventionis to provide a process for the application of vat dyes in which the vat dye is suspended in the water phase of a Water-in-oil emulsion containing atemporary bonding agent which is applied to the textile materials by printing rolls having shallow intaglio engravings, and which after drying is impregnated with a chemical reducing agent comprising an alkali metal hy- -droxide and sodium hydrosulfite which permeates or even dissolves the, resin and'reduces the color 'whereby it is Ehatentecl Oct. 6, 19 59 fixed to the fiber in the same manner as when the vat dye is applied in the conventional printing or dyeing processes. A further object of the invention is to provide a method whereby vat colors can be printed to give sharp prints and faithful reproduction of the engraved designs at high speeds on the conventional textile printing machine,- and to give excellent smoothness in the blotch areas'of the print with a substantial reduction in the cost of printing vat dyes. It is a further object of the invention to produce stable textile printing compositions and concen trates which can be used viseosities, consisting of water-in-oil emulsions in which the vat dye pigment is present in the aqueous phase.

According to the present invention, an aqueous vat dye paste of the type normally employed in printing or dyeing processes and containing a small amount of a dispersing agent, is emulsified into a water-in-oil emulsion previously formed by adding water to a water-immiscible hydrocarbon solvent which contains small amounts of a resin dissolved and/ or colloidally dispersed therein. This vat dye printing paste is then applied to the textile material from the conventional textile printing equipment and conventional shallow engraved intaglio rolls which may be run at higher speeds than when employing the aqueous thickened vat dye pastes. After printing on the textile material, the prints are dried by conventional methods. Subsequently, the prints are impregnated in any conventional type of dye padder with a solution of caustic alkali and sodium hydrosulfite which may contain.

a wetting agent (and, if desired, a thickening agent), and then led immediately into an air-free steam atmosphere at a temperature between 212 F. and 290 F. for periods of from 7 to 30 seconds. The printed clothis thenoxidized and soaped by conventional methods, whereby the dye is converted back to the oxidized form and fixed in the fibers. During the soaping and scouring treatment, the resin which has been permeated or solubilized by the action of the caustic alkali and hydrosulfite is at least in part and usually substantially removed from the fabric.

The prints thus obtained are sharp in outline, smooth, and outstanding in strength and brightness, and at least as fast to light, washing and crocking as prints of the same dyes made by conventional vat dye procedure. In

fabrics with other types of dyes, either in an aqueous system or in an oil-in-water system, when colors are employed which are not affected by the caustic and hydro treatment of thevat dye or where they can be resisted by the presence of oxidizing agents in the printing paste.

The cost of printing by this method is materially reduced since the color value' obtained is considerably greater than the color value obtained in the conventional vat dye printing process, and the process permits higher productivity of the printing equipment. Since the pastes contain no alkali or reducing agent, they may be stored for prolonged periods of time without deterioration. I V a The present invention also contemplates the preparation of novel printing compositions which are particularly applicable for use in the method of printing above described. The invention also contemplates the preparation of water-in-oil color concentrates containing the vat dye pigment in the aqueous phase in relatively high concentrations, which concentrates at the time of use can be diluted with a clear water-in-oil emulsion'vehicle to give the desired concentration for the particularpri'nt sas such or diluted to printing in that it may be em is incorporated into a previously formed water-in-oil emulsion hereinafter referred to as the W/O clear, or they may be produced from a previously prepared waterin-oil emulsion color concentrate in which the aqueous dye paste has been emulsified with a water-immiscible solvent together with dispersing agents and thickeners such as resins, etc.

The aqueous dye pastes which are usually incorporated in the water-in-oil emulsion to produce the emulsion printing pastes normally contain from 8% to 25% color solids and may contain from 1% to 10% of a dispersing agent or agents and other miscellaneous additives norwater-immiscible hydrocarbon solvents. These color concentrates will contain up to 25 color which is dispersed in the aqueous phase. In general these color conof resin, from to 12 parts of pine oil or turpentine,

phase which 1n turn contains from 5 to 25 parts of vat dye (dry basis) and from 0 to 6 parts of a dispersing agent, the balance being water.

The W/O clear will usually consist of from 20% to 35% of a hydrocarbon solvent such as Varsol No. 2, or similar solvent to which is added from 2 to 7 parts by weight of an alkyd or other type resin dissolved in an aromatic hydrocarbon such as xylene, giving an actual resin concentration in the solution of from 1.2% to 4.2%, and from 58% to 78% by Weight of water. Mixed hydrocarbon solvents of course may be employed, and

oil, etc., may be added to confer desirable characteristics It is usually desired to add a small amount of an alkali metal carbonate to neutralize any acidity that may be presen Usually the addition of small amounts of neutral salts such as sodium chloride will increase the viscosity of the emulsion.

dye paste or the water-in-oil emulsion color concentrate is added. It will be obvious to those skilled in the art The preferred class of resins for use in the pre aration of these water-in-oil emulsion pastes are the alkyd resins,

pose of this invention are soluble in aqueous alkaline reducing solutions at 212 F. As examples of this tvpe of resin, mention may be made of the Rohm & Haas Duraplex A-27, which is an alkyd resin made by using approximately 42% phthalic anhydride and 37% cotton seed oil, the. balance being'the conventional polyhydric alcohol such as glycerin, glycol, etc., or those resins'modified with other oils such as soya bean oil, etc., as further (iii illustrated in the examples. Usually these resins will be incorporated in the form of an organic solvent solution, since they are usually soluble in organic solvents and particularly in aromatic hydrocarbon solvents. Other resins such as the epoxy resins, melamine-formaldehyde resins, ureaformaldehyde resins, methacrylate resins, and the styrene-modified alkyd resins are illustrative of the types that may be employed, although, as stated above, the alkyd resins are preferred. Where resins are employed which are difficult to emulsify, it is usually advantageous to use small amounts of the alkyd resins as emulsifying agents. Other emulsifying agents, however, may be employed with these resins, such as esters of fatty acids, for example, lauric, palmitic or stearic acid esters of sorbitan and other alcohols, diethylaminoethylmethacrylate polymers, of copolymers of diethylaminoethylmethacrylate with fatty alcohol methacrylates such as Lorol methacrylate.

The organic water-immiscible solvent forming the oil phase of the water-in-oil emulsion paste (either color concentrate or W/O clear) should be one having a kauributanol value of from 40 to so that the resin will have the desired degree of solubility in this oil. The preferred oils are those which have a high flash point, to reduce hazards in the printing process, and should be readily removable by washing or volatilized during the drying operation. The preferred class of organic solvents is the hydrocarbon solvents of the aliphatic, naphthenic and aromatic series, or mixtures of the same.

high speed agitation or by merely mixing a color concening paste may be obtained by adding basic nitrogen-containing copolymer dispersing agents of the type described Percent Vat dye (dry) 0.02 to 6.0 Resin 1.0 to 4.5 Total dispersing agents 0.00015 to 3.0 Total organic solvent 20.0 to 35.0 Water 78.98 to 51.5

In the above formula it is to be understood that when the basic nitrogen-containing dispersing agent above mentioned is used in the printing paste, it should not be to an erably of the aliphatic type, although it may contain high percentages of naphthenics and/ or aromatics. Aromatic solvents such as solvent naphtha, xylene, and other aro-v matic solvents of this type, may be employed as the water immiscible phase.

of 25 microns.

It is preferred, however, that the aqueous droplets in the emulsion should not be greater than 16 microns.

The vat dye pastes used in the following examples are commercial standard vat dye pastes which contain from 0.075% to 1.5% of the dispersing agent generally referred to as the naphthalene sulfonic acid-formaldehyde condensation product or Leu'canol.

The following examples are given to illustrate the invention, it being understood that the invention is not limited thereto. The parts used are by weight, unless otherwise specified.

. Example 1 (a) Three (3) parts of a xylene solution of a cotton seed oil modified alkyd resin (60% resin solids) of the type currently sold by Rohm & Haas under the designation Duraplex A-27 is colloidally dispersed in 32 parts of a liquid hydrocarbon having a kauri-butanol value of 43.5, available on the market as Varsol No. 2. This dispersion is emulsified with 65 parts of water, using a high speed homogenizer such as the Eppenbach mixer. The water-in-oil emulsion thus obtained has a viscosity of 1000 centipoises at 77 F. when determined in a Brookfield viscosimeter, Model LVF, employing a No. 4 spindle at 12 r.p.m. This emulsion is a light-colored, viscous paste. The alkyd resin employed in this example is made using 42% phthalic anhydride, 37% cotton seed oil, the balance being the conventional polyhydric alcohol such as glycerin, glycol, etc. As a 60% solution in xylene, this solution has a Gardner-Holdt viscosity. rating of Z-7 and an acid number (of the solids) of 510.

(b) Ten parts of a vat dye paste containing 19 weight percent color solids of a vat dye having Prototype No. 522 (as indicated in AATTC Technical Manual, 1955) is added to 90 parts of emulsion (a), using a high-. speed mechanical homogenizer. The stable emulsion which is obtained is the printing paste.

(c) The printing paste of (b) is printed on cotton muslin fabric from an engraved copper roller. The printed fabric is then dried on hot cans for 1 to 5 minutes at from 220 to 275 F. The color-fugitive print is then developed by padding with an alkaline reducing solution which contains 4% by weight of caustic (sodium hydroxide), 6% by Weight of sodium hydrosulfite, 0.1%. by weight of a high fatty alcohol sodium sulfate surface active agent having a chain of from 8 to 10 carbon atoms, and about 1% by Weight of alkali-compatible starch. Within a fraction of a second, the fabric is passed through the above chemical-pad liquor and squeeze rolls, and then directly into an air-free steamer. During the 7 to 30 seconds that the fabric is in the steamer at from 214 to 290 F., the vat dye is reduced to its leuco form and fixed in the fiber. The prints are then finished by oxidiz ing the leuco form to the final insoluble vat dye by passing the fabric through 2% by weight of a hydrogen perox ide solution which is 16.5% by weight active oxygen, and 2% by weight of glacial acetic acid at 140 F. for 1 minute. The printed fabric is then scoured in 0.5% by weight of sodium oleate solution at 180 F. for 10 minutes, rinsed with clear water, and dried.

The tinctorial observed visually is equal to that obtained on application" of a conventional aqueous paste (starch-sodium alginate thickener) containing 13.3 parts of the previously mentioned vat dye paste (Prototype printing paste. Fastness to all common color-destroying agents, such as light, washing and crocking, is equal or superior to the pastes.

Example 2 When 10 parts of the following vat dye pastes are used in the emulsion and the process described in Example 1, the tinctorial value of the resulting prints as above observed visually is equal to that obtained on application value of the resulting navy blue print as No. 522) per 100 parts:

fastness obtained with the aqueous color Tlnctorial Equiva- Colour Percent lent, Parts Dye Dye Paste (10 parts) Index olor Paste in Conven- No. Solids tional Aqueous System Example 3 An emulsion is prepared as described in Example 1, except that 2 parts of turpentine is added to an alkyd resin (3 parts)-liquid hydrocarbon (30 parts) dispersion. The resulting emulsion has a viscosity of 1440 centipoises at 78 F. as determined in the viscosimeter described in Example 1.

When 10 parts of the following vat dye pastes are incorporated with the printing process described in Example 1(a) is carried out, the tinctorial value of the resulting prints as observed visually is equal to that obtained on application of a conventional aqueous paste containing greater than 10 parts of the same dye paste per parts of printing paste. Fastness to all common color-destroying agents, such as light, washing and crocking, is equal to or superior to the fastness obtained with the aqueous An emulsion is prepared as described in Example 1, except that 2 parts of pine oil is added to an alkyd resin (3 parts)-liquid hydrocarbon (30 parts) dispersion as used in Example 1. The resulting emulsion has a viscosity of 1400 centipoises at 77 F. as determined in the viscosimeter described inExample 1.

When 10 parts of the following vat dye pastes are incorporated with 90 parts of the above emulsion and the printing process described in Example 1 is carried out, the tinctorial value of the resulting prints as observed visually is equal to that obtained on application of a conventional aqueous paste containing greater than 10 parts of the same dye paste per 100 parts of printing paste. Fastness to all common color-destroying agents, such as light, washing and crocking, is equal or superior to the fastness obtained with the. aqueous color paste.

Three (3) parts of soya bean oil modified alkyd resin (a 60% resin solids in xylene reaction product of soya bean oil and phthalic anhydride in such proportions that;

parts of the above emulsion and v the :complex reaction product contains 43% of chemically combined .soya' bean oil and the equivalent of 52% of glycerol phthalate and unreacted' ihydroxyl groups equivalentlto of glycerin) having a' Gardner-Holdt viscosity rating of Y-Zl and the resin solids of which has an acid number of 59, is colloidally dispersed in 30 parts of a liquid hydrocarbon having a kauri-butanol value of 43.5 (Varsol No. 2) and 2 parts of turpentine. The dispersion is emulsified with 65 parts of water by high speed agitation such as obtained with an Eppenbach mixer. The resulting water-in-oil emulsion has a viscosity of 440 centipoises at 77 F. as determined in the viscosimeter described in Example 1. When parts of a vat dye paste containing 11.2% by .weight color solids of Jade Green (Colour Index 1101) is incorporated with 90 parts of the above identified alkyd resin-hydrocarbon emulsion and printed as described under the procedure given in Example 1(a), the tinctorial value of the resulting Jade Green print as observed visually is equal to that obtained on application of a conventional aqueous paste containing 11.8 parts of the same dye paste per 100 parts of printing paste. Fastness to all common color-destroying agents, such as light, washing and crocking, is equal or superior to the fastness obtained with the aqueous color paste.

Example 6 An emulsion is prepared as described in Example 1, except that 9 parts of the alkyd resin (60% solids) are employed together with 24 parts of the liquid hydrocarbon and 2 parts of turpentine. When emulsified as in Example 1, this gives a clear emulsion having a viscosity of 400 centipoises at 77 F.

When 10 parts of a standard paste of an orange dyestutf, PR parts color solids, is emulsified with 90 parts of the above emulsion and the resulting water-in-oil emulsion is printed on cotton muslin fabric and developed in accordance with the procedure outlined in Example 1, clear, sharp prints are obtained which exhibit fastness properties equal to or greater than the same vat color when printed by conventional aqueous paste printing methods.

commercial vat dye 381, containing 10.4

Example 7 A W/O clear emulsion is prepared according to Example 1 paragraph (a), substituting for the 32 parts of the particular liquid hydrocarbon 30 parts of solvent naphtha having a kauri-butanol value of 95, and 2 parts of turpentine. The resulting emulsion has a viscosity of 340 centipoises at 76 F.

When 10 parts of a standard commercial vat dye paste of the green dye of Colour Index 1101 containing 11.2% solids is emulsified with 90 parts of the above W/O clear. a stable water-in-oil emulsion printing paste is obtained which, when printed and developed by the process of Example 1 on spun rayon fabric, filament rayon fabric, mercerized broadcloth and dobby drapery fabric, gives prints of excellent fastness properties, sharpness of design and smoothness comparable to the prints of the foregoing examples.

Example 8 (a) Three (3) parts of a xylene solution of a cotton seed oil modified alkyd resin (60% resin solids), as used in Example 1, is mixed with 2 parts of pine oil and is colloidally dispersed in 21 parts of the liquid hydrocarbon used in Example 1. This dispersion is emulsified with 65 parts of water, using an Eppenbach homogenizer. A viscous, water-in-oil emulsion is obtained. (b) Eighty (80) parts of a 40% solution of a copolymer prepared by copolymerizing 90 parts of Lorol fatty alcohol methacrylate and 10 parts of diethylaminoethyl methacrylate dissolved in a light petroleum lubricating oil, are emulsified in parts of water in the presence of 5 parts of an ethylene oxide condensation product of an' aralkyl phenol dispersing agent (Igepal CA).

(0) 0.5 part of the oil-in-water dispersion (b) is added to an aqueous paste consisting of 8.746 parts of water and:

0.662 part of a Green dye, O1. 1101 0.216 part of a Green dye, PR 293 0.176 part of a Yellow dye, PR 9 which has been prepared by mixing the necessary amounts of the standard commercial vat dye pastes. This dye concentrate is added during vigorous mixing to 69.7 parts of the W/O clear prepared in paragraph (a) above. A viscous, stable water-in-oil emulsion printing paste is obtained.

' The above printing paste is printed on x 80 cotton print cloth from shallow intaglio engraved copper printing rollers in a conventional textile printing machine and dried on conventional drying equipment at about 250 F. Subsequently, the fabric is impregnated at an liquid pick-up with a 5% caustic soda-5% sodium hydrosulfite solution contained in a conventional dye padder threaded to give a single dip and single nip. The fabric is then immediately led into an air-free steam atmosphere at a temperature of 214 F. and steamed for 13' seconds, rinsed, oxidized and soaped in open width. An excellent sharp, smooth, fast green print is obtained.

Examples 9 to 13, inclusive, illustrate the preparation of color concentrates which can be readily mixed with the W/O clears at the time of printing by the use of simple mechanical agitators, since the color concentrate and W/O clear are already in a highly emulsified state and can be easily mixed. It is of course understood that the final mixture may be further diluted with the solvent under normal mixing conditions or with water under high speed homogenization.

The color concentrates which are pigmented water-inoil emulsions contain preferably from 25% to 50% by weight of the oil phase and 75% to 50% of the aqueous phase. The oil phase will usually contain from 1.8% to 6% of the alkyd or other resin and up to 12% of pine oil, the balance being the organic solvent. 7 aqueous phase will contain from 5% to 20% of vat dye solids and up to 0.6% of a dispersing agent ormixture of dispersing agents such as the naphthalene sulfonic acidformaldehyde sodium salt, sodium lignin sulfonate, or the nitrogen-containing copolymer dispersing agents described above.

Example 9 (a) 600 parts of a press cake containing 33.5% of the dye of Colour Index 1101 is pasted with 2.0 parts of soda ash and 148 parts of water in a Werner-Pfieiderer mill until smooth.

The resulting aqueous phase is homogenized'into an oil phase consisting of parts of Duraplex A-27 resin solution (60% solids), 60 parts of pine oil and parts of Varsol No. 2, using a high speed homogenizer such as the Eppenbach homomixer. The resulting waterin-oil emulsion is a smooth paste and contains 20% vat dye solids. These are located in the aqueous phase, i.e., they do not flush into the oil phase. I

(b) A concentrated unpigmented or clear emulsion is prepared by Eppenbach-homogenizing the solution of 5 g. soda ash and 20 g. common salt in 375 g. water into a mixture of 500 g. Duraplex A-27 resin solutionand 100 g. pine-oil.

(c) A smooth print paste is prepared by mixing 50,

of the color concentrate described in paragraph (a) with 50 g. of the clear concentrate described in paragraph (b), 300 g. Sunoco Spirits hydrocarbon solvent and 600 g. of water. 7 V V The resulting printing paste is printed on cotton muslin fabric from an engraved copper roller by the method described in paragraph (c) of Example 1. 'The'tinctorial' The- on similar application of an aqueous printing Example 500 grams of the vat dye paste of PR 381 containing 11.2% dye solids and 0.6% naphthalene sulfonic acidformaldehyde sodium salt dispersing agent (dry basis) is .pasted with 2 grams of soda ash and 98 grams of water by stirring manually. The resulting aqueous phase 1s homogenized, using the Eppenbach homomixer, into 400 grams 'of an oil phase consisting of 90 grams of Duraplex A-27 resin solution, 60 grams of pine oil and 250 grams of hydrocarbon solvent such as Varsol No. 2.

The resulting thick, smooth paste contains 5.6% vat dye solids. A smooth printing paste is prepared by mixing 50 grams of this color concentrate with 50 grams of the concentrated unpigmented emulsion described in paragraph (b) of Example 9, 300 grams of Varsol No. 2 hydrocarbon solvent (Esso) and 600 grams of water. The resulting printing paste is printed on cotton muslin by the method described in paragraph (c) of Example 1. The tinctorial value of the orange print produced with this emulsion printing paste is equal to that obtained on application of a conventional aqueous paste (starch-gum tragacanth thickener) containing more vat dye solids of PR 381; in shade it is noticeably brighter than the aqueous system print. Fastness of the two prints to all common color-destroying agencies is essentially equal.

Example 11 500 grams of vat dye paste containing 11.2% of vat dye of PR 381 and 0.6% of naphthalene sulfonic acidiormaldehyde sodium salt is pasted with 2.0 grams of soda ash.

The resulting dispersion is homogenized (using an Eppenbach homomixer) into an oil phase containing 90 grams'of Duraplex A-27 resin solution, '60 grams of turpentine and 348 grams of hydrocarbon solvent such as Varsol No. 2.

The resulting smooth vat dye pigmented emulsion contains 5.6% vat dye solids located in the aqueous phase. It is conv'ertedto a printing paste by the method described in Example 10. Its tinctorial value is equal to that obtained using the emulsion printing paste of Example 10, that is equal to that obtained using the aqueous printing paste of 15% greater color solids. Fastness of the-corresponding comparative prints is essentially equal.

Example 12 500 grams of the khaki dye paste, PR 122, containing approximately 22% vat dye Solids, 0.9% naphthalene sulfonic acid-forrnaldehyde sodium salt, and 0.2% partially desulfonated sodium lignin sulfonate is suspended 'in 200 grams of water; This dispersion is added while mixing with an Eppenbach homogenizer to an oil phase consisting of 30 grams of Duraplex A-27 resin solu-- tion, grams of pine oil and 250 grams of hydrocarbon solvent such as Varsol No. 2. Mixing is continued for approximately five minutes to form a stiff smooth paste that contains approximately 11.0% vat dye solids. The vat dye is still located in the aqueous phase after homogenization.

When this concentrated pigmented emulsion is converted to a printing paste in the manner employed in Example 10 and printed on cotton muslin by the method described in paragraph (c) of Example 1, it yields prints tinctorially equal to but sharper and better covered than those obtained from a conventional starch-gum tragacanth-thickened aqueous system of equal pigment concentration. The prints are equal in fastness'.

.710 Example 13 220' grams of the vat dye used in Example 12 is dispersed in 480 grams of water. While Eppenbach homogenizing, this dispersion is added to an oil phase containing 100 grams of Duraplex A-27 resin solution, 120 grams of pine oil and 80 grams of Varsol No. 2.

, The resulting concentrated emulsion contains in the aqueous phase 4.8% vat dye solids on the weight of the total emulsion. A printing paste produced from thisemulsion by the method described in Example 12 also yields prints which are equal in tinctorial strength and in fastness to, but sharper and better covered than, one. prepared from a conventional starch-tragacanth-thickened 15 aqueous system of equal pigment concentration.

types of resin as the The following examples illustrate the use, of various temporary binder for the pigment.

Example 14 13.7 parts of a blended resin consisting of equal parts (1) An unmodified liquid epoxy resin having a viscosity of v10,000 to 14,000 centipoises [Brookfield viscometen. 23 C. (73

7 F.)] and an epoxy value of 0.480 eq./100 g.,.e.g., Araldite Liquid Resin No. 6010 marketed by Ciba Company, Inc.; v V V .(2) an unmodified liquid epoxy resin having a viscosity of 20,000 to 40,000 centipoises [Brookfield viscometer, 23 C. (73 F.)] and an epoxy value of 0440-0480 eq./100 g., e.g., Araldite Liquid Resin No. 6020, is mixed with 1.3 parts of a xylene solution of a cottonseed oil modified alkyd resin (60% resin solids) having a viscosity of.35,000 to 40,000 centipoises. The mixture is then .dispersedin 12.5 parts of a liquid hydrocarbon having akauri-butanol value of 97.9 available on the market as Solvesso xylol. This dispersion is emulsifiedusing a high-speed mixer'with 72.5 parts of water in which has been dissolved 2.0 g./l. common salt and 0.25 g./l. sodium carbonate. The water-in-oil emulsion thus obtained has aviscosity of 39,000 centipoises at 77 .15. when determined with a Brookfield viscometer, Model LVF,

' employing a No. 4 spindle at 12 r.p.m. This emulsion is a white-colored, viscous paste. I

Ten (10) parts of a commercial vat dye paste having 19.1% color solids of a vat dye having Colour Index .1113, is added to parts of the above emulsion, using a high-speedmechanical'homogenizer. The stable emulsion which is obtained is the printing paste.

This printing paste is printed, developed and finished on cotton muslin fabric by the process described in Example 1. The tinctorial value of the resulting bright blue print as observed visually, is equal to that obtained on application of a conventional aqueous paste (starch-sodium alginate thickener) containing 25 parts of the previously mentioned vat dye paste (C1. 1113) per parts of printing paste.

- 7 Example 15 Six (6) parts of a petroleum spirits solution of a. styrene-modified alkyd resin (50% resin solids) of the type currently sold by American Cyanamid Company under the designation Cycopol S10l1 is colloidally dispersed in 29.5 parts of a liquid hydrocarbon having a kauri-butanol value of 43.5 available on the market as Varsol No. 2. This dispersion is emulsified with 64.5 parts of aqueous solution containing 2.0 g./l. common salt and 0.25 g./l. sodium carbonate, using an Eppenbach homomixer. The water-in-oil emulsion thus obtained has a Viscosity of 11,500 centipoises at 77 F. when determined with a Brookfield viscometer, Model LVF, employing a No. 4 spindle at 12 r.p.m. This emulsion is a lightcolored, viscous paste. The alkyd resin employed in this example is a 50% solution in petroleum spirits, having a Gardner color value of 36 and a Gardner-Holdt viscosity rating of Z Z at 77 F. (25 C.).

" Ten (10) parts of a commercial vat dye Paste having 19.1% color solids of a vat dye having Colour Index 1113 is added to 90 parts of the above emulsion, using a highspeed mechanical homogenizer. The stable emulsion which is obtained is the printing paste. a

The tinctorial value of the resulting bright blue print as observed visually is equal to that obtained on application of a conventional aqueous paste (starch-sodium .alginate thickener) containing 16.7 parts of the previously mentioned vat dye paste (C.I. 1113) per 100 parts of printing paste.

Example 16 Nine (9) parts of a 60:40 butanolzxylene solution of a melamine-formaldehyde resin (50% resin solids) of the type currently sold by American Cyanamid Company under the designation Melmac 245-8, is blended with 1 part of a xylene solution of a cottonseed oil modified alkyd resin (60% resin solids). The mixture is colloidally dispersed in 20 parts of ,a liquid hydrocarbon having a kauri-butanol value of 43.5, available on the market as Varsol No. 2. This dispersion is emulsified, using a high-speed mixer with 70 parts of water in which has been dissolved 2.0 g./l. of common salt and 0.25 g./l. of sodium carbonate. The water-in-oil emulsion thus obtainel has a viscosity of 34,000 centipoises at 77 F. when determined with a Brookfield viscometer, Model LVF, employing a No. 4 spindle at 12 rpm. The emulsion is a lightcolored viscous paste. The melamine-formaldehyde 'resin employed is a 50% solution and has a Gardner- Holdt viscosity of L at 77 F. (25 C.) and the solid resin has an acid number maximum 1.

Ten parts of a vat dye paste containing 11% color solids of the vat dye of Cl. 1101 is added to '90 parts of the above emulsion, using a high-speed mechanical homogenizer. The stable emulsion which is obtained is the printing paste. The printing paste is printed, developed and finished on cotton muslin fabric by the process described in Example 1.

The tinctorial value of the resulting blue-green print, as observed visually, is equal to that obtained on similar application of a conventional aqueous paste (starch-sodium alginate thickener) containing 25 ,parts of the previously mentioned vat dye paste (C.I. 1101) per 100 parts of printing paste.

When the alkyd resin of this example is replaced by from 0.125 to 0.5 parts of diethylaminoethylmethacrylate per part of the melamine-formaldehyde resin, a satisfactory emulsion is produced and the same desirable tinctorial value of the color is obtained in printing by the same method. The diethylaminoethylmethacrylate in this case is used as the dispersing agent for-the melamineformaldehyde resin.

Example 17 7.5 parts of a 40% solution of a copolymer prepared by copolymerizing 90 parts of Lorol fatty alcohol methacrylate and 10 parts of diethylaminoethyl methacrylate dissolved in a light petroleum lubricating oil, is dispersed in 1. parts of a liquid hydrocarbon having a kauributanol value of 97.9, available on the market as Solvesso xylol, and 20.0 parts of a second liquid hydrocarbon having a kauri-butanol value of 43.5 available on the market as Varsol No. 2. This dispersion is emulsified with 71.0 parts of water in which has been dissolved 2.0 g./l. of common salt, 2.0 g./l. of sodium'sorbitol borate and 0.25 g./l. of sodium carbonate, using a highspeed mixer such as the Eppenbach mixer. The water-inoil emulsion thus obtained has a viscosity of 1000 centipoises at 77 F. when determined in a Brookfield viscometer, Model LVF, employing a No. 4 spindle at 12 rpm. This emulsion is a light-colored viscous paste.

Ten (10) parts of a commercial vat dye paste'of the blue dye C.I. 1113 is added to 90 parts of the above emulsion, using a high speed mechanical homogenizet'. The stable emulsion which is obtained is the printing paste.

' 3 The above printing pasteis printed, developed and finished on cotton muslin'fabric by the process described in Example 1, giving a tinctor'ial value of the resulting blue print as observed visually, equal to that obtained on similar application of a conventional aqueous paste (starch-sodium alginate thickener) containing 20 parts of the same dye paste per 100 parts of printing paste.

The printing compositions and processes of printing of this invention may be employed in the printing of any cellulosic textile material or other textiles which can normally be dyed with vat dyes in the customary manner, namely, those which are not deleteriously aitected by caustic alkalies in the concentrations and at the temperatures employed in the development of the vat dye.

The water-in-oil emulsion printing pastes of the present invention may be applied to textile materials from engraved rolls, plates or by screen printing techniques. The application may be in patterns of single or multiple colors, overall application to solid shades, and either on one or both sides of the fabrics.

'I claim:

1. In the process for printing textile materials with vat dyes in which the vat dye is subsequently developed with caustic alkali and an alkali metal hydrosulfite, the steps which comprise printing the vat dye on the textile material in the form of a water and oil emulsion in which the vat dye pigment is dispersed in a water phase and the oil phase contains from 1.0% to 4.5% of a caustic alkali-permeable resin of the group consisting of oil modified alkyd resins, epoxy resins, melamine formaldehyde resins, urea formaldehyde resins, methacrylate resins, and styrene-modified alkyd resins, the total amount of organic solvent in the emulsion comprising from 20.0% to 35.0%, the amount of water in the total amount comprising from 78.98% to 51.5% and the amount of dye present on a dry basis being from 0.02% to 6.0%, the organic solvent of the emulsion being one that has a kauri-butanol value of from 40 to 100, drying the material so printed, padding the dried material with an aqueous solution of a reducing agent consisting of caustic alkali and sodium hydrosulfite, steaming the material so padded in air-free steam at temperatures of from 212' F. to 290 F. for a period of from 7 to 30seconds, oxidizing the reduced vat dye on the textile material, Washing and drying.

2. The process'of claim 1 in which the alkali permeable resin is a drying oil-modified alkyd resin.

3. The process of claim 1 in which the alkali-permeable resin is a cottonseed oil-modified alkyd resin.

4. A water-in-oil dye emulsion for use in vat dye printing consisting essentially of from 25 to 50 parts of an oil phase consisting of an organic water-immiscible solvent having a kauri-butanol value of from 40 to 100 and from to 50 parts of a water phase, the oil phase containing from 1.8 to 6.0 parts of acaustic hydrosulfite-pe'rmeable resin of the group consisting of oil modified alkyd resins, epoxy resins, melamine formaldehyde resins, ur'ea formaldehyde resins, methacrylate resins, and styrenemodified alkyd resins, from 0 to 12 parts of a solvent of the group consisting of pine oil and turpentine, and the balance being a water-immiscible solvent; the aqueous phase containing from 5 to 25 parts of vat dye (dry basis) and from O'to 6 parts of a dispensing agent, the balance being water.

5. A printing paste for use in the coloring of textile materials which may be applied from intaglio rolls of a conventional textile printing machine, consisting essentially of a water-in oil emulsion in which a vat dye is dispersed in the oil phase consisting of an' organic water-immiscible solvent having a kauri-butanol value of from 40 "to and a caustic hydrosulfite-permeable alkyd resin is present in the oil phase, said printing paste having the general composition as-follows: 0.02% to 6.0% of vat dye (dry), 1.0% to 4.5% ofcaustichydrosulfitepermeable alkyd resin, 0.00015% "to 3.0% of total dis persing agents, 20.0% to 35.0% total organic solvent, and from 78.98% to 51.5% of Water.

6. A printing paste for use in the coloring of textile materials which may be applied from intaglio rolls of a conventional textile printing machine, prepared by incorporating an aqueous vat dye paste containing a small amount of a water-soluble dispersing agent in an oil emulsion containing a caustic hydrosulfite-permeable alkyd resin, which oil emulsion contains from 20% to 35% of a hydrocarbon solvent having a kauri-butanol value of from 40 to 95, from 58% to 78% and from 1.2% to 4.2% by weight of an alkyd resin, and a small amount of an oil-soluble dispersing agent, said oil emulsion prior to the addition of the dye paste by weight of water References Cited in the file of this patent UNITED STATES PATENTS 2,288,261 Abrams June 30, 1942 2,323,871 Kienle July 6, 1943 2,587,905 Saville Mar. 4, 1952 2,594,899 Fordemwalt Apr. 29, 1952 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noe 2,967,624 October 6,, 1959 Arthur Kn .Saville It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

C l m 3, l 4 for "75 F0 5 read 75 F t 5 column 11, lines 23 and 24, for "obtains-l" read obtained w line' 58, for "19 parts" read 1.5 parts column 12, line 63,. for "dispensing" read dispersing Signed and sealed this 12th day of April 1960,

(SEAL) Attest:

KARL H, XL ROBERT C. WATSON Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noe 2,907,624 October 6 1959 Arthur Kn .Saville It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 3, line 46, for "75 F0 4=- 5 read 75 F0 1 ,5 column 11, lines 23 and 24, for "Obtainel read an obtained e line 58, for "1. parts" read w 105 parts column 12,.1ine 6 for "dispensing" read dispersing A Signed and sealed this 12th day of April 1960a (SEAL) Attest:

KARL E. AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. IN THE PROCESS FOR PRINTING TEXTILE MATERIALS WITH VAT DYES IN WHICH THE VAT DYE IS SUBSEQUENTLY DEVELOPED WITH CAUSTIC ALKALI AND AN ALKALI METAL HYDROSULFITE, THE STEPS WHICH COMPRISE PRINTING THE VAT DYE ON THE TEXTILE MATERIAL IN THE FORM OF A WATER AND OIL EMULSION IN WHICH THE VAT DYE PIGMENTS IS DISPERSED IN A WATER PHASE AND THE OIL PHASE CONTAINS FROM 1.0% TO 4.5% OF A CAUSTIC ALKALI-PERMEABLE RESIN OF THE GROUP CONSISTING OF OIL MODIFIED ALKYD RESINS, EPOXY RESINS, MELAMINE FORMALDEHYDE RESINS, UREA FORMALDEHYDE RESINS, METHACRYLATE RESINS, AND STYRENE-MODIFIED ALKYD RESINS, THE TOTAL AMOUNT OF ORGANIC SOLVENT IN THE EMULSION COMPRISING FROM 20.0% TO 35.5%, THE AMOUNT OF WATER IN THE TOTAL AMOUNT COMPRISING FROM 78.98% TO 51.5% AND THE AMOUNT OF DYE PRESENT ON A DRY BASIS BEING FROM 0.02% TO 6.0%, THE ORGANIC SOLVENT OF THE EMULSION BEING ONE THAT HAS A KAURI-BUTANOL VALUE OF FROM 40 TO 100, DRYING THE MATERIAL SO PRINTED, PADDING THE DRIED MATERIAL WITH AN AQUEOUS SOLUTION OF A REDUCING AGENT CONSISTING OF CAUSTIC AL KALI AND SODIUM HYDROSULFITE, STEAMING THE MATERIAL SO PADDED IN AIR-FREE STEAM AT TEMPERATURE OF FROM 212* F. TO 290*F. FOR A PERIOD OF FROM 7 TO 30 SECONDS, OXIDIZING THE REDUCED VAT DYE ON THE TEXTILE MATERIAL, WASHING AND DRYING. 